Abstract
Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A preference for protons at sp 2 carbons was observed with conversions up to >90% and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol-1 for the H/D exchange at the β-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe 2 donor sites) and real catalysts (PtBu2 donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol-1, indicating H/D exchange at the β-position of naphthalene to be clearly favoured over the α-position, which is in full accordance with the experimental observations.
Original language | English |
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Pages (from-to) | 3493-3500 |
Number of pages | 8 |
Journal | European Journal of Inorganic Chemistry |
Issue number | 22 |
DOIs | |
Publication status | Published - Aug 2008 |
Keywords
- CH activation
- DFT calculations
- Deuteration
- H/D exchange
- Ruthenium dihydrogen complexes
ASJC Scopus subject areas
- Inorganic Chemistry